EP1421036A1 - Single step laydown method of making dry fiber with complex fluorine doped profile - Google Patents

Single step laydown method of making dry fiber with complex fluorine doped profile

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Publication number
EP1421036A1
EP1421036A1 EP02746557A EP02746557A EP1421036A1 EP 1421036 A1 EP1421036 A1 EP 1421036A1 EP 02746557 A EP02746557 A EP 02746557A EP 02746557 A EP02746557 A EP 02746557A EP 1421036 A1 EP1421036 A1 EP 1421036A1
Authority
EP
European Patent Office
Prior art keywords
stripping
preform
dopant
forming
moat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02746557A
Other languages
German (de)
French (fr)
Inventor
Steven B. Dawes
Michael T. Murtagh
Pushkar Tandon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Publication of EP1421036A1 publication Critical patent/EP1421036A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
    • C03B37/023—Fibres composed of different sorts of glass, e.g. glass optical fibres, made by the double crucible technique
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/036—Optical fibres with cladding with or without a coating core or cladding comprising multiple layers
    • G02B6/03616—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference
    • G02B6/03622—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference having 2 layers only
    • G02B6/03627—Optical fibres characterised both by the number of different refractive index layers around the central core segment, i.e. around the innermost high index core layer, and their relative refractive index difference having 2 layers only arranged - +
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/012—Manufacture of preforms for drawing fibres or filaments
    • C03B37/014—Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
    • C03B37/01446—Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
    • C03B2201/12—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2203/00—Fibre product details, e.g. structure, shape
    • C03B2203/10—Internal structure or shape details
    • C03B2203/22—Radial profile of refractive index, composition or softening point
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/028—Optical fibres with cladding with or without a coating with core or cladding having graded refractive index
    • G02B6/0283—Graded index region external to the central core segment, e.g. sloping layer or triangular or trapezoidal layer

Definitions

  • the present invention relates generally to the manufacture of optical waveguide fibers, and in particular to manufacturing a fluorine doped preform from which an optical fiber may be drawn.
  • Optical fibers having a fluorine doped region have unique attributes for long haul optical fibers, dispersion compensating optical fibers, dispersion slope compensating optical fibers, and high data rate optical fibers.
  • the ability to include fluorine in an optical waveguide preform is an important aspect of producing an optical fiber with a fluorine doped region.
  • Prior attempts to incorporate fluorine into a preform include depositing fluorine doped soot on a starting member or bait rod.
  • the starting member is a sintered core cane.
  • the deposited fluorine exhibits significant migration from the region or regions of interest and migration into areas not intended to include the dopant.
  • Preforms fluorinated during deposition have also exhibited a fluorine loss of between forty percent (40%) to fifty percent (50%) during consolidation.
  • One reason for the low retention rate of fluorine is the production of the compound SiF 4 during deposition.
  • Fluo ⁇ ne may also be added to a soot preform du ⁇ ng a consolidation doping step as taught in Berkey U.S. No. 4,629,485.
  • soot is deposited on a core cane forming a physical interface between a central core region of the optical fiber and the soot region.
  • the soot coated, core cane is d ⁇ ed in a 2% chlo ⁇ ne containing atmosphere for approximately 2 hours at 1000°C.
  • the d ⁇ ed preform is then exposed to a fluo ⁇ ne containing atmosphere for 1-4 hours at a temperature of between 1100°C and 1400°C.
  • the fluo ⁇ ne doped preform is then fully sintered. Subsequently, the preform is drawn into an optical fiber. This method adds unnecessary time and steps to the manufactu ⁇ ng of the preform, as well as additional costs thereto.
  • fluo ⁇ ne doping du ⁇ ng laydown is preferred as it is possible to make more complex profiles in a reduced number of steps.
  • fluo ⁇ ne doping du ⁇ ng laydown is plagued with the problem of fluo ⁇ ne migration into areas where fluo ⁇ ne doping is not intended.
  • the use of glass banner layers has been used to prevent the migration of fluo ⁇ ne.
  • the use of glass barrier layers on both sides of a fluo ⁇ ne doped region may cause water to be trapped within the contained layer. Any water within the contained layer that cannot be removed using conventional drying procedures, i.e., since it is trapped between the glass banner layers, may lead to an unacceptably high attenuation within the resultant optical fibers.
  • This invention meets the need for a method for producing preforms having at least one fluorine doped region which does not exhibit significant signal loss via attenuation, and eliminates the detrimental effects of fluorine migration.
  • One embodiment of the present invention is to provide a method for manufacturing an optical waveguide preform including forming a preformed body including a first portion and a second portion, wherein the second portion includes a dopant, and wherein the first portion exhibits a density greater than the second portion. The method further includes stripping at least a portion of the dopant from at least a section of the second portion.
  • Another embodiment of the present invention is to provide a method for manufacturing an optical fiber preform including forming a preform body including a moat and a radial portion abutting the moat, wherein the portion includes a fluorine dopant. The method further includes stripping substantially all of the fluorine dopant from the radial portion.
  • embodiments of the methods disclosed herein include applying heat to a portion of the preform body, thereby forming a glass barrier between two regions of the preform, drying certain radial portions or regions of the preform with a drying agent, partially sintering the portions prior to the stripping step, and stripping the dopant from a particular portion via a stripping agent.
  • FIG. 1 is a cross-sectional schematic view of an optical waveguide preform embodying the present invention and a soot producing burner;
  • Fig. 2 is a diagram of an optical fiber refractive index profile constructed from the preform, wherein the preform does not exhibit migration;
  • Fig. 3 is a cross-sectional schematic view of the preform and a heat source
  • Fig. 4 is a cross-sectional schematic view of the preform located vertically within a sintering oven
  • Fig. 5 is a diagram of an optical fiber refractive index profile constructed from a preform, which exhibits migration
  • Fig. 6 is a cross-sectional schematic view of an optical waveguide fiber constructed from the preform; and Fig. 7 is a diagram of an optical waveguide fiber refractive index profile of the optical fiber of Fig. 6.
  • a soot preform 10 is formed from a Chemical Vapor
  • preform 10 can be formed by various CVD processes such as Outside Vapor Deposition (“OVD”) process, Vapor Axial Deposition (“VAD”) process, a Modified Chemical Vapor Deposition (“MCVD”) process, and a Plasma Chemical Vapor Deposition (“PCVD”) process.
  • OCVD Outside Vapor Deposition
  • VAD Vapor Axial Deposition
  • MCVD Modified Chemical Vapor Deposition
  • PCVD Plasma Chemical Vapor Deposition
  • an amount of soot 12 is deposited via an OVD process, from a burner 14 onto a starting member or bait rod 16 and a glass handle 17 to form preform 10, and is preferably formed in a single deposition step.
  • the soot 12 being deposited onto starting member 16 is a silica based soot.
  • preform 10 may have one or more regions of doped silica soot. Dopants utilized within the regions of preform 10 include, but are not limited to, Ge, P,
  • Preform 10 may also have one or more regions of undoped silica soot. In the present example, it is most preferred that an outer region of preform 10 comprises undoped silica soot. In one preferred embodiment, preform 10 includes a first region or portion 20, a second region or radial portion 22 sunounding first region 20, and a third region or radial portion 24 surrounding second region 22. The refractive index profile of an optical waveguide fiber constructed form preform 10 is shown in
  • preform 10 is formed by depositing first region 20 of silica soot doped with a refractive index increasing dopant, such as germanium (e.g., having a ⁇ i), depositing second region 22 of silica soot doped with a refractive index decreasing dopant such as fluorine (e.g., having a ⁇ 2 ), and depositing third region 24 of pure silica soot (e.g., having a ⁇ 3 ).
  • the refractive index profile of the present example generally follows the relationship of ⁇ > ⁇ 3 > ⁇ 2 , however, other profiles may be constructed utilizing the concepts disclosed herein.
  • the method Prior to depositing the soot of second region 22, the method includes applying heat from a heat source 26 (Fig. 3) to an outer surface of first region 20, thereby "fire polishing" or forming a glass barrier layer 28 that radially sunounds first region 20.
  • Heat source 26 includes a burner system 30 that generates a flame 32 by combusting fuels including, but not limited to, oxygen, methane and oxygen, carbon monoxide and oxygen, deuterium, hydrogen, and combinations thereof. It should be noted that heat source 26 may also include other systems capable of heating the first region 20 to form glass barrier layer 28, such as CO 2 lasers and plasma torches. Preferably, glass barrier layer 28 is formed to a thickness within the range of between about 50 ⁇ m and about 100 ⁇ m.
  • the method for manufacturing preform 10 next includes depositing second region 22 onto glass barrier layer 28 of first region 20.
  • soot 12 utilized to form second region 22 includes fluorine as a dopant therein. More preferably, second region 22 includes at least about 0.3 wt.% fluorine therein. However, second region 22 may include various dopants as listed above.
  • the method next includes depositing the third region 24 of silica based soot onto second region 22. In the present example, third region 24 is preferably substantially free of the fluorine dopant. As illustrated in Fig.
  • the refractive index profile of an optical waveguide fiber resulting from preform 10 subsequent to the deposition of soot 12 to form third region 24 shows a decrease of ⁇ between first region 20 and second region 22, and a inciease of ⁇ between second legion 22 and third region 24 It should be noted that the profile as shown in Fig 2 does not include any migration of fluo ⁇ ne into third region 24
  • the soot preform 10 (Fig 4) is then suspended in a sinte ⁇ ng furnace 34 As illustrated in Fig 4, a ball joint 36 is attached to handle 17 Perform 10 also includes a center passageway 40 from within which the starting member 16 is removed, and a plug 42 with an optional capillary tube 44. It should be noted that plug 42 and ball joint 36 are not required to practice the present invention
  • soot preform 10 is heat treated in furnace 34 in an atmosphere preferably substantially devoid of any halide containing compound to a first temperature, after an optional drying step, wherein soot preform 12 is introduced to a drying agent, including, but not limited to, chlo ⁇ ne, germanium chloride, germanium tetrachlo ⁇ de, silicate tetrachlo ⁇ de, and combinations thereof Du ⁇ ng the drying step, the drying agent is circulated about preform 10 by passing the drying agent through the center passageway 40 as indicated by a directional arrow 35, and about the exterior of preform 10 as indicated by directional arrows 37.
  • the atmosphere after drying comp ⁇ ses an inert atmosphere, such as an atmosphere of helium, argon, nitrogen, or mixtures thereof
  • soot preform 10 is partially sintered by exposing the preform 10 to a first cente ⁇ ng temperature
  • the first or partially sinte ⁇ ng temperature comp ⁇ ses a temperature of within the range of from about 900°C to about 1350°C.
  • the partial sintenng temperature is above about 1240°C, more preferably above about 1280°C, and most preferably above about 1300°C.
  • preform 10 is maintained at the first sinte ⁇ ng temperature for at least about thirty (30) minutes, and more preferably at least about forty-five (45) minutes It is further prefened that the heating step lasts for a sufficient pe ⁇ od of time such that preform 10 reaches an isothermal temperatuie.
  • Isothermal temperature desc ⁇ bes a preform without a radial temperature gradient that is greater than about 5°C/cm, more preferably not greater than about 2°C/cm, and most preferably about 0°C/cm
  • germanium contained within first legion 20 is pievented from migrating into second region 22 by glass barrier layer 28, while fluorine doped within second region 22 is prevented from migrating to within first region 20 by glass banner layer 28.
  • fluorine doped within second region 22 migrates into third region 24, thereby resulting in an approximate profile as shown in Fig. 5, that would be exhibited by an optical waveguide fiber drawn from soot preform 10 subsequent to the partial sintering step.
  • the method next includes ramping the temperature within furnace 34 from the partially sintering temperature to a high or complete sintering temperature of around 1450°C, thereby completely sintering preform 10.
  • a stripping agent is introduced into furnace 34 that strips away the fluorine that has migrated from second region 22 to within third region 24.
  • the stripping agent utilized to strip the unwanted dopant from within third region 24 of preform 10, which in the present example is fluorine, comprises a compound including an element selected from a group of VA and/or VIA in the periodic table of elements. Group VA and VIA elements form volatile compounds when reacted with fluorine, and can compete effectively with silicon for the fluorine on the basis of very high bond strengths with fluorine. For example, at 1500°K, the reaction:
  • the reaction to form POF 3 goes forward even while stripping fluorine from SiF 4 .
  • ⁇ G f for species such as SiO 3/2 F are not readily available, but since the silicon oxyfluorides spontaneously decompose to SiF 4 and silica at temperatures above 1300°K, it is safe to say that ⁇ G f (SiO x F y )> ⁇ G f (SiF 4 ) so that the reaction above describes an upper limit for the reaction energy for stripping fluorine from fluorinated silica.
  • the stripping agent preferably includes POCl 3 .
  • the approximate refractive index profile an optical waveguide fiber 46 (Fig. 6) resulting from preform 10 after being completely sintered is shown in Fig. 7.
  • Fiber 46 includes a core region 48, a moat or first radial portion 22 sunounding core region 20, and an overclad or second radial portion 24 surrounding first radial portion 22, which correspond to first region 20, second region 22 and third region 24 of soot preform 10.
  • the partial sintering temperature utilized to partially sinter soot preform 10, the specific stripping agent, the complete sintering temperature used to completely center soot preform 10, as well as the associated dwell times may be chosen to optimize and control the "penetration depth" of the stripping agent into third region 24 of preform 10.
  • the amount of the stripping agent used and the temperature at which the stripping agent is introduced is determined by the location of the moat- overclad interface. These parameters were chosen such that the stripping agent strips only the unwanted fluorine in the overclad and not from the moat.
  • the stripping reaction takes place under conditions where the reaction and sintering rates are much faster than the diffusion rates such that the stripping agent is able to diffuse through only the overclad region of the blank.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
  • Glass Compositions (AREA)

Abstract

The method is directed to making an optical fiber with a complex profile. First a preform (10) is made having a doped first portion (20), a barrier layer (28) and a second portion (22 and 24) doped with fluorine. Then the fluorine is removed prom a part (24) of the second portion.

Description

SINGLE STEP LAYDOWN METHOD OF MAKING DRY FIBER
WITH COMPLEX FLUORINE DOPED PROFILE
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the manufacture of optical waveguide fibers, and in particular to manufacturing a fluorine doped preform from which an optical fiber may be drawn.
2. Technical Background
Optical fibers having a fluorine doped region have unique attributes for long haul optical fibers, dispersion compensating optical fibers, dispersion slope compensating optical fibers, and high data rate optical fibers. The ability to include fluorine in an optical waveguide preform is an important aspect of producing an optical fiber with a fluorine doped region.
Prior attempts to incorporate fluorine into a preform include depositing fluorine doped soot on a starting member or bait rod. Typically, the starting member is a sintered core cane. One of the drawbacks of this approach is that the deposited fluorine exhibits significant migration from the region or regions of interest and migration into areas not intended to include the dopant. Preforms fluorinated during deposition have also exhibited a fluorine loss of between forty percent (40%) to fifty percent (50%) during consolidation. One reason for the low retention rate of fluorine is the production of the compound SiF4 during deposition. Typically, SiF generated during deposition will volatilize from the piefoπn duπng consolidation As a result, the time of consolidation must be extended in an effort to redope the preform with SιF4 The relatively long times at the relatively low temperatures of the slow ramp consolidation impact fluoπne retention in at least two ways. (1) the fluoπne containing vapor (ma ly SιF4) evolving from the soot has sufficient time to diffuse out of the preform; and (2) the equi bπum of redoping the preform with SιF4 vapor is not a favored reaction at the lower temperatures and low ramp rates. Thus, deposition of fluoπnated soot with a redoping step has not proven to be effective
Fluoπne may also be added to a soot preform duπng a consolidation doping step as taught in Berkey U.S. No. 4,629,485. In one such consolidation doping process, soot is deposited on a core cane forming a physical interface between a central core region of the optical fiber and the soot region. The soot coated, core cane is dπed in a 2% chloπne containing atmosphere for approximately 2 hours at 1000°C. The dπed preform is then exposed to a fluoπne containing atmosphere for 1-4 hours at a temperature of between 1100°C and 1400°C. The fluoπne doped preform is then fully sintered. Subsequently, the preform is drawn into an optical fiber. This method adds unnecessary time and steps to the manufactuπng of the preform, as well as additional costs thereto.
While doping has been demonstrated duπng the consolidation process, fluoπne doping duπng laydown is preferred as it is possible to make more complex profiles in a reduced number of steps. As noted above, fluoπne doping duπng laydown is plagued with the problem of fluoπne migration into areas where fluoπne doping is not intended. The use of glass banner layers has been used to prevent the migration of fluoπne. However, the use of glass barrier layers on both sides of a fluoπne doped region may cause water to be trapped within the contained layer. Any water within the contained layer that cannot be removed using conventional drying procedures, i.e., since it is trapped between the glass banner layers, may lead to an unacceptably high attenuation within the resultant optical fibers.
A need exists for alternative methods to produce preforms having at least one fluoπne doped legion which does not exhibit significant migiation of fluorine in the preform oi high attenuation in the fiber SUMMARY OF THE INVENTION
This invention meets the need for a method for producing preforms having at least one fluorine doped region which does not exhibit significant signal loss via attenuation, and eliminates the detrimental effects of fluorine migration. One embodiment of the present invention is to provide a method for manufacturing an optical waveguide preform including forming a preformed body including a first portion and a second portion, wherein the second portion includes a dopant, and wherein the first portion exhibits a density greater than the second portion. The method further includes stripping at least a portion of the dopant from at least a section of the second portion.
Another embodiment of the present invention is to provide a method for manufacturing an optical fiber preform including forming a preform body including a moat and a radial portion abutting the moat, wherein the portion includes a fluorine dopant. The method further includes stripping substantially all of the fluorine dopant from the radial portion.
In addition, embodiments of the methods disclosed herein include applying heat to a portion of the preform body, thereby forming a glass barrier between two regions of the preform, drying certain radial portions or regions of the preform with a drying agent, partially sintering the portions prior to the stripping step, and stripping the dopant from a particular portion via a stripping agent.
Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional schematic view of an optical waveguide preform embodying the present invention and a soot producing burner;
Fig. 2 is a diagram of an optical fiber refractive index profile constructed from the preform, wherein the preform does not exhibit migration;
Fig. 3 is a cross-sectional schematic view of the preform and a heat source; Fig. 4 is a cross-sectional schematic view of the preform located vertically within a sintering oven; Fig. 5 is a diagram of an optical fiber refractive index profile constructed from a preform, which exhibits migration;
Fig. 6 is a cross-sectional schematic view of an optical waveguide fiber constructed from the preform; and Fig. 7 is a diagram of an optical waveguide fiber refractive index profile of the optical fiber of Fig. 6.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Additional features and advantages of the invention will be set forth in the detailed description which follows and will be apparent to those skilled in the art from the description or recognized by practicing the invention as described in the following description together with the claims and appended drawings.
It is to be understood that the foregoing description is exemplary of the invention only and is intended to provide an overview and an understanding of the nature and character of the invention as it is defined in the claims. The accompanying drawings are included to provide a further understanding of the invention and are incorporated and constitute part of the specification. The drawings illustrate various features and embodiments of the invention which, together with their description, serve to explain the principles and operation of the invention. A soot preform 10, as shown in Fig. 1, is formed from a Chemical Vapor
Deposition ("CVD") process. It should be noted that preform 10 can be formed by various CVD processes such as Outside Vapor Deposition ("OVD") process, Vapor Axial Deposition ("VAD") process, a Modified Chemical Vapor Deposition ("MCVD") process, and a Plasma Chemical Vapor Deposition ("PCVD") process. In the example illustrated in Fig. 1, an amount of soot 12 is deposited via an OVD process, from a burner 14 onto a starting member or bait rod 16 and a glass handle 17 to form preform 10, and is preferably formed in a single deposition step.
Preferably, the soot 12 being deposited onto starting member 16 is a silica based soot. More preferably, preform 10 may have one or more regions of doped silica soot. Dopants utilized within the regions of preform 10 include, but are not limited to, Ge, P,
Al, B, Ga, In, Sb, Er, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, Se, Te, Fr, Ra, Bi, or combination thereof. Preform 10 may also have one or more regions of undoped silica soot. In the present example, it is most preferred that an outer region of preform 10 comprises undoped silica soot. In one preferred embodiment, preform 10 includes a first region or portion 20, a second region or radial portion 22 sunounding first region 20, and a third region or radial portion 24 surrounding second region 22. The refractive index profile of an optical waveguide fiber constructed form preform 10 is shown in
Fig. 2. In the present example, preform 10 is formed by depositing first region 20 of silica soot doped with a refractive index increasing dopant, such as germanium (e.g., having a Δi), depositing second region 22 of silica soot doped with a refractive index decreasing dopant such as fluorine (e.g., having a Δ2), and depositing third region 24 of pure silica soot (e.g., having a Δ3). The refractive index profile of the present example generally follows the relationship of Δι>Δ3>Δ2, however, other profiles may be constructed utilizing the concepts disclosed herein.
Prior to depositing the soot of second region 22, the method includes applying heat from a heat source 26 (Fig. 3) to an outer surface of first region 20, thereby "fire polishing" or forming a glass barrier layer 28 that radially sunounds first region 20.
Heat source 26 includes a burner system 30 that generates a flame 32 by combusting fuels including, but not limited to, oxygen, methane and oxygen, carbon monoxide and oxygen, deuterium, hydrogen, and combinations thereof. It should be noted that heat source 26 may also include other systems capable of heating the first region 20 to form glass barrier layer 28, such as CO2 lasers and plasma torches. Preferably, glass barrier layer 28 is formed to a thickness within the range of between about 50 μm and about 100 μm.
Again, referring to Fig. 1, the method for manufacturing preform 10 next includes depositing second region 22 onto glass barrier layer 28 of first region 20. In the present example, soot 12 utilized to form second region 22 includes fluorine as a dopant therein. More preferably, second region 22 includes at least about 0.3 wt.% fluorine therein. However, second region 22 may include various dopants as listed above. The method next includes depositing the third region 24 of silica based soot onto second region 22. In the present example, third region 24 is preferably substantially free of the fluorine dopant. As illustrated in Fig. 2, the refractive index profile of an optical waveguide fiber resulting from preform 10 subsequent to the deposition of soot 12 to form third region 24 shows a decrease of Δ between first region 20 and second region 22, and a inciease of Δ between second legion 22 and third region 24 It should be noted that the profile as shown in Fig 2 does not include any migration of fluoπne into third region 24
The soot preform 10 (Fig 4) is then suspended in a sinteπng furnace 34 As illustrated in Fig 4, a ball joint 36 is attached to handle 17 Perform 10 also includes a center passageway 40 from within which the starting member 16 is removed, and a plug 42 with an optional capillary tube 44. It should be noted that plug 42 and ball joint 36 are not required to practice the present invention
In a preferred embodiment, soot preform 10 is heat treated in furnace 34 in an atmosphere preferably substantially devoid of any halide containing compound to a first temperature, after an optional drying step, wherein soot preform 12 is introduced to a drying agent, including, but not limited to, chloπne, germanium chloride, germanium tetrachloπde, silicate tetrachloπde, and combinations thereof Duπng the drying step, the drying agent is circulated about preform 10 by passing the drying agent through the center passageway 40 as indicated by a directional arrow 35, and about the exterior of preform 10 as indicated by directional arrows 37. Preferably, the atmosphere after drying compπses an inert atmosphere, such as an atmosphere of helium, argon, nitrogen, or mixtures thereof
Initially, soot preform 10 is partially sintered by exposing the preform 10 to a first centeπng temperature The first or partially sinteπng temperature compπses a temperature of within the range of from about 900°C to about 1350°C. Preferably, the partial sintenng temperature is above about 1240°C, more preferably above about 1280°C, and most preferably above about 1300°C. It is also preferred that the temperature is not above about 1350°C Preferably, preform 10 is maintained at the first sinteπng temperature for at least about thirty (30) minutes, and more preferably at least about forty-five (45) minutes It is further prefened that the heating step lasts for a sufficient peπod of time such that preform 10 reaches an isothermal temperatuie. Isothermal temperature as used herein descπbes a preform without a radial temperature gradient that is greater than about 5°C/cm, more preferably not greater than about 2°C/cm, and most preferably about 0°C/cm
In the illustrated example, as the soot pieform 10 is dπed and partially sinteied, germanium contained within first legion 20 is pievented from migrating into second region 22 by glass barrier layer 28, while fluorine doped within second region 22 is prevented from migrating to within first region 20 by glass banner layer 28. During the drying and partial sintering steps, fluorine doped within second region 22 migrates into third region 24, thereby resulting in an approximate profile as shown in Fig. 5, that would be exhibited by an optical waveguide fiber drawn from soot preform 10 subsequent to the partial sintering step.
The method next includes ramping the temperature within furnace 34 from the partially sintering temperature to a high or complete sintering temperature of around 1450°C, thereby completely sintering preform 10. During this final step, a stripping agent is introduced into furnace 34 that strips away the fluorine that has migrated from second region 22 to within third region 24. The stripping agent utilized to strip the unwanted dopant from within third region 24 of preform 10, which in the present example is fluorine, comprises a compound including an element selected from a group of VA and/or VIA in the periodic table of elements. Group VA and VIA elements form volatile compounds when reacted with fluorine, and can compete effectively with silicon for the fluorine on the basis of very high bond strengths with fluorine. For example, at 1500°K, the reaction:
1/3 POCl3 + V* SiF4 + Vi O2 == 1/3 POF3 + V* SiO2 + Vτ Cl2, has a ΔG of -8.5 Kcal per mole. The reaction to form POF3 goes forward even while stripping fluorine from SiF4. ΔGf for species such as SiO3/2F are not readily available, but since the silicon oxyfluorides spontaneously decompose to SiF4 and silica at temperatures above 1300°K, it is safe to say that ΔGf (SiOxFy)> ΔGf (SiF4) so that the reaction above describes an upper limit for the reaction energy for stripping fluorine from fluorinated silica. In the present example, the stripping agent preferably includes POCl3. The approximate refractive index profile an optical waveguide fiber 46 (Fig. 6) resulting from preform 10 after being completely sintered is shown in Fig. 7. Fiber 46 includes a core region 48, a moat or first radial portion 22 sunounding core region 20, and an overclad or second radial portion 24 surrounding first radial portion 22, which correspond to first region 20, second region 22 and third region 24 of soot preform 10. It should be noted that the partial sintering temperature utilized to partially sinter soot preform 10, the specific stripping agent, the complete sintering temperature used to completely center soot preform 10, as well as the associated dwell times may be chosen to optimize and control the "penetration depth" of the stripping agent into third region 24 of preform 10. The amount of the stripping agent used and the temperature at which the stripping agent is introduced is determined by the location of the moat- overclad interface. These parameters were chosen such that the stripping agent strips only the unwanted fluorine in the overclad and not from the moat. The stripping reaction takes place under conditions where the reaction and sintering rates are much faster than the diffusion rates such that the stripping agent is able to diffuse through only the overclad region of the blank.
It will become apparent to those skilled in the art that various modifications to the preferred embodiment of the invention as described herein can be made without departing from the spirit or scope of the invention as defined by the appended claims.

Claims

The invention claimed is:
1. A method of manufacturing an optical waveguide preform, comprising: forming a preform including a first portion and a second portion, the second portion including a dopant therein, and wherein the first portion exhibits a density greater than the second portion; and stripping the dopant from at least a section of the second portion.
2. The method of claim 1 wherein the dopant stripped from the section originated from dopant migration in a previous step.
3. The method of claim 1 wherein the dopant in the second portion comprises fluorine.
4. The method of claim 3 wherein the dopant in the second portion comprises an average weight percent of at least 0.3% fluorine substantially throughout the second portion prior to the step of stripping.
5. The method of claim 4 wherein the step of stripping is accomplished by a stripping agent.
6. The method of claim 5 wherein the stripping agent comprises a compound including an element selected from a group consisting of VA and VIA in the periodic table of elements.
7. The method of claim 6 wherein the stripping agent is selected from a group including phosphorous oxychloride, phosphorous trichloride, sulfur oxychloride, antimony, arsenic, chlorides and oxychlorides.
8. The method of claim 7 wherein the step of forming the preform body includes doping the first portion with germanium.
9. The method of claim 8, further including: applying heat to the first portion prior to forming the second portion, thereby causing at least a portion of the first portion to have a greater density than the second portion.
10. The method of claim 9 wherein the heat applying step includes heating the first portion with a flame generated utilizing at least one fuel selected from a group including oxygen, methane and oxygen, carbon monoxide and oxygen, deuterium, and hydrogen.
11. The method of claim 9 wherein the heat applying step includes heating the first portion with a CO2 laser.
12. The method of claim 9 wherein the heat applying step includes heating the first portion with a plasma torch.
13. The method of claim 9 wherein the heat applying step is accomplished within the range of from about 1500°C to about 1700°C.
14. The method of claim 9 wherein the heat applying step includes forming a glass barrier between the first portion and the second portion.
15. The method of claim 9 further including: drying the first and second portions with a drying agent.
16. The method of claim 15 wherein the drying step includes selecting the drying agent from a group including chlorine, germanium chloride, germanium tetrachloride, silicon tetrachloride, and combinations thereof.
17. The method of claim 15 further including: partially sintering the first and second portions prior to the stripping step.
18. The method of claim 1 wherein the step of stripping is accomplished by a stripping agent that includes an element selected from a group consisting of VA and VIA in the periodic table of elements.
19. The method of claim 1, wherein the step of forming the preform body includes doping the first portion with germanium.
20. The method of claim 1, further including: applying heat to the first portion prior to forming the second portion, thereby causing at least a portion of the first portion to have a greater density than the second portion.
21. The method of claim 20, wherein the heat applying step includes forming a glass barrier between the first portion and the second portion.
22. The method of claim 21, further including: drying the first and second portions with a drying agent.
23. The method of claim 22, further including: partially sintering the first and second portions prior to the stripping step.
24. The method of claim 1 wherein the stripping step includes stripping nearly all of the dopant from a section of the second portion.
25. The method of claim 1 wherein the step of stripping includes stripping substantially all migrated dopant from an outer section of the second portion.
26. A method of manufacturing an optical fiber preform, comprising: forming a preform including a moat and radial portion abutting the moat, wherein the moat and the radial portion include a fluorine dopant; and stripping substantially all the fluorine dopant from the radial portion.
27. The method of claim 26 wherein the step of stripping is accomplished by a stripping agent.
28. The method of claim 27 wherein the stripping agent comprises a compound including an element selected from a group including VA and VIA in the periodic table
of elements.
29. The method of claim 28 wherein the stripping agent includes selecting the stripping agent from a group including phosphorous oxychloride, phosphorous trichloride, sulfur oxychloride, antimony, arsenic, chlorides and oxychlorides.
30. The method of claim 29 wherein the preform forming step includes forming the preform to include a core region surrounded by the moat.
31. The method of claim 30, further including: applying heat to the core region prior to forming the moat, thereby causing the core region to have at least a portion exhibiting a greater density than the moat.
32. The method of claim 31 wherein the heat applying step includes heating the core region with a flame generated utilizing at least one fuel selected from a group including oxygen, methane and oxygen, carbon monoxide and oxygen, deuterium, and hydrogen.
33. The method of claim 31 wherein the heat applying step includes heating the core region with a CO2 laser.
34. The method of claim 31 wherein the heat applying step includes heating the core region with a plasma torch.
35. The method of claim 31 wherein the heat applying step includes forming a glass barrier between the core region and the moat.
36. The method of claim 31, further including: drying the preform body with a drying agent.
37. The method of claim 36 wherein the drying step includes selecting the drying agent from a group including chlorine, germanium chloride, germanium tetrachloride, silicate tetrachloride, and combinations thereof.
38. The method of claim 31, further including: partially sintering the preform prior to the stripping step.
39. The method of claim 26 wherein the step of stripping is accomplished by a stripping agent comprising a compound including an element selected from a group including VA and VIA in the periodic table of elements.
40. The method of claim 26 wherein the preform body forming step includes forming the preform body to include a core region sunOunded by the moat.
41. The method of claim 40, further including: applying heat to the core region prior to forming the moat, thereby causing the core region to have at least a portion exhibiting a greater density than the moat.
42. The method of claim 41, further including: drying the preform body with a drying agent.
43. The method of claim 42, further including: partially sintering the preform body prior to the stripping step.
44. The method of claim 26 wherein the dopant in the radial portion is provided as a result of migration of the dopant from the moat.
EP02746557A 2001-07-30 2002-06-17 Single step laydown method of making dry fiber with complex fluorine doped profile Withdrawn EP1421036A1 (en)

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US09/918,088 US6843076B2 (en) 2001-07-30 2001-07-30 Single step laydown method of making dry fiber with complex fluorine doped profile
US918088 2001-07-30
PCT/US2002/019157 WO2003011780A1 (en) 2001-07-30 2002-06-17 Single step laydown method of making dry fiber with complex fluorine doped profile

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US20030046960A1 (en) 2003-03-13
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US6843076B2 (en) 2005-01-18
WO2003011780A1 (en) 2003-02-13

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